CN104968748B - Alkoxy-functional organopolysiloxane resins and polymer and its related forming method - Google Patents
Alkoxy-functional organopolysiloxane resins and polymer and its related forming method Download PDFInfo
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- CN104968748B CN104968748B CN201480007143.3A CN201480007143A CN104968748B CN 104968748 B CN104968748 B CN 104968748B CN 201480007143 A CN201480007143 A CN 201480007143A CN 104968748 B CN104968748 B CN 104968748B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
Abstract
The present invention discloses a kind of alkoxy-functional organopolysiloxane resins and polymer, and which includes the product of the reaction of following components：I () includes R3SiO1/2Unit and SiO4/2The alkenyl functional silicone resin of unit；(ii) there are the functionalized with alkoxysilane organosilicone compounds of the hydrogen atom of at least one silicon bonding in molecular end；(iii) according to formula R2 3Si‑(R2 2SiO)s‑SiR2 2H or R2 3Si‑(R2 2SiO)t‑(HR2SiO)‑SiR2 3Or the end-capping reagent of its combination；And (iv) each molecule averagely has the polysiloxane of at least 2 aliphatic series unsaturation organic groups, the reaction is carried out in the presence of (v) hydrosilylation catalysts.In the alkoxy-functional organopolysiloxane resins and polymer, each R2It independently is alkyl and subscript s and t independently has the value in the range of 0 to 10.
Description
Technical field
Present invention relates generally to reaction resin and polymer, and more particularly, it is related to alkoxy-functionalization organic
Polyorganosiloxane resin and polymer.
Background technology
The constituent polyorganosiloxane composition for being solidified into elastomeric material is well known.Such composition can be by will be with can
Solidification (for example, hydrolyzable, radiation-hardenable or thermal curable) group polydiorganosiloxanepolyurea and cross-linking agent and/or according to
The catalyst of needs mixes and prepares.In general, polydiorganosiloxanepolyurea can be reactive with 1 to 3 in each chain end
Group.Then compositionss comprising these components for example can be solidified by being exposed to atmospheric water.
Additionally, for the practicality for showing to apply some, such as silicone adhesive application, filler can be added
(for example, increase stretching with the physical performance characteristics for improving the gained cured product of compositionss in constituent polyorganosiloxane composition
Intensity and increase elongation at break %).Other properties (such as adhesiveness and allocability) also should for binding agent in compositionss
Effect is played in terms of performance and business acceptance.
As for allocability, generally include resin in silicone adhesive application so that compositionss are more easy to flowing, and because
This can reduce adhesive composition webbing, such as when being allocated to which by sharp mouth applicator.These resins are in combination
In thing can be non-reacted (that is, being non-reacted resin) or can be reactive (that is, being reaction resin) and with
The other components reaction of compositionss, such as during solidification process.
The content of the invention
It is an object of the present invention to provide a kind of novel chemically-reactive resin and polymer, which can be introduced into silicone adhesive group
Other beneficial effect is provided in compound and in terms of mobility, the engineering propertiess for improving and cure response.
The present invention discloses a kind of alkoxy-functional organopolysiloxane resins and polymer, and which includes the anti-of following components
The product answered：I () includes R3SiO1/2Unit and SiO4/2The alkenyl functional silicone resin of unit；(ii) at molecule end
The functionalized with alkoxysilane organosilicone compounds of hydrogen atom of the end with least one silicon bonding；(iii) end-capping reagent；With
And polysiloxane of (iv) each molecule averagely with least 2 aliphatic series unsaturation organic groups, the reaction is in (v) hydrogenation
Carry out in the presence of silylation catalyst.
In the present invention, each R of alkenyl functional silicone resin independently is the unit price with 1 to 6 carbon atom
Alkyl, on condition that at least one R is thiazolinyl.Additionally, R3SiO1/2Unit and SiO4/2The mol ratio of unit has 0.5/1 to 1.5/
Value in the range of 1.
The end-capping reagent (iii) of the present invention is according to formula R2 3SiO-(R2 2SiO)s-SiR2 2H or R2 3SiO-(R2 2SiO)t-
(HR2SiO)-SiR2 3Or its combination, wherein each R2It independently is alkyl and wherein subscript s and t independently has 0 to 10 model
Value in enclosing.
The alkoxy-functional organopolysiloxane resins and polymer of the present invention can be used for diversified organosilicon and glue
Mixture application.Alkoxy-functional organopolysiloxane polymer and resin contribute to the allocability of these binding agents, and
The reactive functional groups for being capable of moisturecuring are also provided.
Invention additionally discloses a kind of method for forming alkoxy-functional organopolysiloxane resins and polymer, including：
(1) while reacting following components：
I () includes R3SiO1/2Unit and SiO4/2The alkenyl functional silicone resin of unit, wherein each R independently are
Univalence hydrocarbyl with 1 to 6 carbon atom, on condition that at least one R is thiazolinyl,
Wherein described R3SiO1/2Unit and SiO4/2The mol ratio of unit has 0.5/1 to 1.5/1 value,
(ii) there is the functionalized with alkoxysilane organosiloxane of the hydrogen atom of at least one silicon bonding in molecular end
Compound,
(iii) according to formula R2 3SiO-(R2 2SiO)s-SiR2 2H or R2 3SiO-(R2 2SiO)t-(HR2SiO)-SiR2 3Or its group
The end-capping reagent of conjunction, wherein each R2It independently is alkyl and wherein subscript s and t has the value in the range of 0 to 10 respectively,
(iv) polysiloxane of each molecule averagely with least 2 aliphatic series unsaturation organic groups；And
(v) hydrosilylation catalysts, to obtain the product of step (1)；And
(2) under vacuo the product of step (1) is stripped to remove any excessive end-capping reagent (iii)
And form the alkoxy-functional organopolysiloxane resins and polymer.
Invention additionally discloses a kind of method for forming alkoxy-functional organopolysiloxane resins and polymer, including：
(1) while reacting following components：
I () includes R3SiO1/2Unit and SiO4/2The alkenyl functional silicone resin of unit, wherein each R independently are
Univalence hydrocarbyl with 1 to 6 carbon atom, on condition that at least one R is thiazolinyl and wherein described R3SiO1/2Unit with
SiO4/2The mol ratio of unit has 0.5/1 to 1.5/1 value,
(iii) according to formula R2 3SiO-(R2 2SiO)s-SiR2 2H or R2 3SiO-(R2 2SiO)t-(HR2SiO)-SiR2 3Or its group
The end-capping reagent of conjunction, wherein each R2It independently is alkyl and wherein subscript s and t independently has in the range of 0 to 10 respectively
Value,
(iv) polysiloxane of each molecule averagely with least 2 aliphatic series unsaturation organic groups, and
(v) hydrosilylation catalysts, to obtain product；And
(2) (ii) is had the functionalized with alkoxysilane organosilicon of the hydrogen atom of at least one silicon bonding in molecular end
Siloxane compound introduces the product of step (1) and obtains the product of step (2)；And
(3) excessive end-capping reagent (iii) is stripped to form the alkoxyl from the product of step (2) under vacuo
Functionalization organopolysiloxane resins and polymer.
Specific embodiment
Except as otherwise noted, otherwise word " one ", " one kind " and " described " respectively refer to one (one kind) or multiple (various).
Except as otherwise noted, otherwise in the application all amounts, ratio and percentage ratio are by weight.Except as otherwise noted, otherwise institute
There is kinematic viscosity to measure at 25 DEG C.
The present invention relates to one kind can be used for binding agent application (such as silicone adhesive composition) reaction resin and
Polymer.
In certain embodiments, reaction resin and polymer are alkoxy-functional organopolysiloxane resins and polymerization
Thing, which includes the product of the reaction of following components：
I () includes R3SiO1/2Unit and SiO4/2The alkenyl functional silicone resin of unit, wherein each R independently are
Univalence hydrocarbyl with 1 to 6 carbon atom, on condition that at least one R is thiazolinyl,
Wherein R3SiO1/2Unit and SiO4/2The mol ratio of unit has 0.5/1 to 1.5/1 value,
(ii) there is the functionalized with alkoxysilane organosiloxane of the hydrogen atom of at least one silicon bonding in molecular end
Compound；And
(iii) according to formula R2 3SiO-(R2 2SiO)s-SiR2 2H or R2 3SiO-(R2 2SiO)t-(HR2SiO)-SiR2 3Or its group
The end-capping reagent of conjunction, wherein each R2It independently is alkyl and wherein subscript s and t has the value in the range of 0 to 10 respectively；
(iv) polysiloxane of each molecule averagely with least 2 aliphatic series unsaturation organic groups；
The reaction is carried out in the presence of (v) hydrosilylation catalysts.
Alkenyl functional SiClx siloxane compound (i) includes resin portion, wherein R in certain embodiments3SiO1/2Unit
(that is, " M " unit) is bonded to SiO4/2Unit (that is, " Q " unit), the SiO4/2Each of unit be bonded at least one its
He is SiO4/2Unit.In R3SiO1/2In unit, as described above, each R is individually with the monovalent hydrocarbon less than 6 carbon atoms
Base, on condition that at least one R is thiazolinyl.The example of suitable R bases includes alkyl, such as methyl, ethyl, propyl group and amyl group；Alkene
Base, such as vinyl, alkyl and 5- hexenyls；And aryl, such as phenyl.
At least 1/3rd and more preferably essentially all R bases be methyl, on condition that at least one R bases be thiazolinyl, and
In addition on condition that resin (i) is comprising with 0.5 to 4 weight % of gross weight meter of resin (i), or the thiazolinyl of 1.0 to 2.2 weight %
Functional group.In other words, the amount vinyl content of resin (i) is in the range of 0.05 to 4 weight % of resin (i) gross weight.Have
The preferred R of methyl3SiO1/2The example of unit includes Me3SiO1/2Unit and PhMe2SiO1/2Unit, wherein Me are that methyl and Ph are
Phenyl.
Additionally, in certain embodiments, the silanol content of resin (i) is resin (i) gross weight less than 1 weight %.
As defined herein, term " silanol content " refers to the weight of silicon-oh group in the specific molecular comprising silicon-oh group
Amount percentage ratio, and total weight percent defined herein as silicon-oh group in resin (i) (that is, Si-OH groups in resin
Percentage by weight).
For purposes of the present invention, R in resin (i)3SiO1/2Unit and SiO4/2The ratio of unit has 0.5 respectively:1 to
1.5:1 mol ratio.Preferably, total M units of resin (i) and the mol ratio of total Q unit are 0.6:1 and 1.0:Between 1.With
Upper M/Q mol ratios easily can pass through29Si nuclear magnetic resonance, NMR (NMR) spectrographic method is obtained.
Resin (i) preferably has 12,000 to 30,000g/mol (dalton), or 17,000 to 22,000g/mol
In the range of weight average molecular weight Mw。
There is the functionalized with alkoxysilane organosiloxane compound of the hydrogen atom of at least one silicon bonding in molecular end
Thing (ii) has formula HSi (R in certain embodiments3)2OSi(R3)2CH2CH2SiR3 z(OR3)3-z, wherein each R3Independently
Be the monovalent hydrocarbon with 1 to 6 carbon atom and wherein subscript z be 0 or 1.
Or, there is the functionalized with alkoxysilane organosiloxane of the hydrogen atom of at least one silicon bonding in molecular end
Compound (ii) is with formula HSi (Me)2OSi(Me)2CH2CH2Si(OMe)3, wherein Me is methyl.
Component (iii) is end-capping reagent.End-capping reagent can be poly- two organosilicon that each molecule has a silicon bonded hydrogen atom
Oxygen alkane.Exemplary end-capping reagent can have formula (I), formula (II) or its combination.Formula (I) is R2 3SiO-(R2 2SiO)s-SiR2 2H.Each
R2As mentioned above and independently be monovalent hydrocarbon group, its example is alkyl, such as methyl, ethyl, propyl group, butyl, amyl group and oneself
Base；And aryl, such as phenyl, tolyl, xylyl and benzyl；And subscript s has in the range of 0 to 10, or 1 to 10
Value, or be 1.Formula (II) is R2 3SiO-(R2 2SiO)t-(HR2SiO)-SiR2 3.In the formula, each R2It is as mentioned above and independent
Ground be monovalent hydrocarbon group, its example be alkyl, such as methyl, ethyl, propyl group, butyl, amyl group and hexyl；And aryl, such as
Phenyl, tolyl, xylyl and benzyl.Subscript t has the value in the range of 0 to 10, or is 0.
Component (iv) is polysiloxane of each molecule averagely with least 2 aliphatic series unsaturation organic groups, this
A little aliphatic series unsaturation organic groups can occur hydrosilylation reactions with the hydrogen atom of the silicon bonding of component (ii).Component (iv)
There can be straight or branched structure.Or, component (iv) can have linear chain structure.Component (iv) can be comprising two or more
The combination of polysiloxane is planted, these polysiloxane are different at least one of following property：Structure, viscosity,
The degree of polymerization and sequence.
Component (iv) is with the 100 minimum average B configuration degree of polymerization (average DP).Or, the average DP of component (iv) can be 100
To in the range of 1000.The DP distributions of the polysiloxane of component (iv) can be bimodal.For example, component (iv) can be included
A kind of DP is the polydiorganosiloxanepolyamide that the thiazolinyl of the polydiorganosiloxanepolyurea and another kind DP of 60 thiazolinyl end-blocking higher than 100 is blocked
Alkane, on condition that the average DP of these polydiorganosiloxanepolyureas is in the range of 100 to 1000.However, for the conjunction of component (iv)
Suitable polysiloxane is with the 10 minimum degree of polymerization (DP), on condition that polysiloxane of the DP less than 10 is more than with DP
100 polysiloxane combination.The suitable polydiorganosiloxanepolyurea of component (iv) is as known in the art and commercially available
Obtain.For example, DowSFD-128 has the DP, Dow in the range of 800 to 1000SFD-120 has
DP in the range of 600 to 700, Dow7038 have 100 DP, and DowSFD-119 has 150
DP.All these polydimethylsiloxane for being ethenyl blocking, they can be from the road health of Michigan, USA Midland
Ning companies (Dow Corning Corporation of Midland, Michigan, USA) are commercially available.When component (iv) has
When having bimodal distribution, poly- organic higher less than DP of the amount of DP relatively low polysiloxane (low DP polysiloxane)
Siloxanes (high DP polysiloxane).For example, in bimodal distribution, low DP polysiloxane/high DP polysiloxane
Ratio can be in the range of 10/90 to 25/75.
The example of component (iv) is formula (I), the polysiloxane of formula (II) or its combination.In certain embodiments, formula
(I) it is R4 2R5SiO(R4 2SiO)a(R4R5SiO)bSiR4 2R5, and formula (II) is R4 3SiO(R4 2SiO)c(R4R5SiO)dSiR4 3.
In these formulas, each R4The monovalent organic groups without aliphatic degree of unsaturation independently are, each R5It independently is aliphatic unsaturated
Organic group, subscript a have the meansigma methodss in the range of 2 to 1000, and subscript b has the meansigma methodss in the range of 0 to 1000, subscript c
There are the meansigma methodss in the range of 4 to 1000 with the meansigma methodss in the range of 0 to 1000, and subscript d.In formula (I) and (II),
10≤(a+b)≤1000 and 10≤(c+d)≤1000.
R4Suitable monovalent organic groups include but is not limited to monovalent hydrocarbon group, its example be alkyl, such as methyl, second
Base, propyl group, butyl, amyl group, octyl group, undecyl and octadecyl；Cycloalkyl, such as cyclohexyl；And aryl, such as benzene
Base, tolyl, xylyl, benzyl and 2- phenethyls.Each R5It independently is aliphatic unsaturation monovalent organic groups.R5Can be
Aliphatic unsaturation monovalent hydrocarbon group, its example is alkenyl group, such as vinyl, pi-allyl, acrylic and cyclobutenyl；And alkynes
Base group, such as acetenyl and propinyl.
Component (iv) may include polydiorganosiloxanepolyurea, the poly- diformazan that such as i) dimethylvinylsiloxy is blocked
Radical siloxane, ii) dimethylvinylsiloxy end-blocking poly- (dimethyl siloxane/methyl vinyl silicone),
Iii) Polymethyl methacrylate of dimethylvinylsiloxy end-blocking, iv) trimethylsiloxy end-blocking
Poly- (dimethyl siloxane/methyl vinyl silicone), v) trimethylsiloxy end-blocking Polymethyl methacrylate,
Vi) poly- (dimethyl siloxane/methyl phenyl siloxane), the vii of dimethylvinylsiloxy end-blocking) dimethylvinylsiloxy
Base siloxy end-blocking poly- (dimethyl siloxane/diphenyl siloxane), viii) phenyl, methyl, vinyl-monosilane
The polydimethylsiloxane of epoxide end-blocking, ix) polydimethylsiloxane of dimethyhexenes base siloxy end-blocking, x) diformazan
Poly- (dimethyl siloxane/methylhexenylsiloxane), the xi of base hexenylsiloxy end-blocking) dimethyhexenes base first silicon
Alkoxy end-capped poly- methylhexenylsiloxane, xii) trimethylsiloxy end-blocking poly- (dimethyl siloxane/methyl
Hexene radical siloxane), or xiii) its combination.
Component (v) is the hydrosilylation catalysts of the reaction for accelerating component (i)-(iv).Component (v) can be enough to promote
The amount addition of the reaction of component (i)-(iv), and the conjunction of all components used during the amount for example can be enough to provide in this way
Lay equal stress on gauge 0.1ppm (PPM) to 1000ppm, or 1ppm to 500ppm, or 2ppm to 200ppm, or 5ppm
To the platinum group metal of 20ppm.
Suitable hydrosilylation catalysts (v) are as known in the art and commercially available.Component (v) can be comprising choosing
From the platinum group metal of platinum (Pt), rhodium, ruthenium, palladium, osmium or iridium metals, or its organo-metallic compound, or its combination.Component (v)
Example is such as chloroplatinic acid, chloroplatinic acid hexahydrate, the compound of platinous chloride, and the compound is organic with low-molecular-weight
The complex of polysiloxanes, or platinum compounds of the micropackaging in substrate or core-shell type structure.Platinum and the organic poly- silicon of low-molecular-weight
The complex of oxygen alkane includes the complex of 1,3- divinyl -1,1,3,3- tetramethyl disiloxanes and platinum.Or, catalyst can
Complex comprising 1,3- divinyl -1,1,3,3- tetramethyl disiloxanes Yu platinum.When catalyst is that platinum is had with low-molecular-weight
During the complex of machine polysiloxanes, the amount of catalyst in this way in component used combined wt meter can 0.04% to
In the range of 0.4%.
The suitable hydrosilylation catalysts of component (v) in such as United States Patent (USP) 3,159,601,3,220,972,3,
296,291st, 3,419,593,3,516,946,3,814,730,3,989,668,4,784,879,5,036,117 and 5,175,
It is described in 325 and EP 0 347 895 B.
In certain embodiments, the amount vinyl content contributed by component (i) and (iv) in reaction resin and polymer is (i.e.,
Contents of ethylene) account for 0.6 to 2.2 weight % of reaction resin and total polymer weight, or 1.0 to 2.0 weight %.
In certain embodiments, the silanol content contributed by component (ii) in reaction resin and polymer accounts for reactivity
0.3 to 2.2 weight % of resin and total polymer weight, or 1.0 to 2.0 weight %.
In certain embodiments, reaction resin and polymer, wherein at most 60 weight % of the thiazolinyl of resin (i) are prepared
With the atomic reaction of hydrogen of the silicon bonding of compound (ii).In certain embodiments, reaction resin and polymer are prepared, wherein setting
The atomic reaction of hydrogen of at least 40 weight % of the thiazolinyl of fat (i) and the silicon bonding of end-capping reagent (iii).
In addition to component (i)-(v), reaction resin and polymer can also include other optional components.It is available suitable
Other component include but is not limited to (vi) acid scavenger, (vii) coloring agent, (viii) resin treatment, (ix) resist,
(x) viscosifier and combinations thereof.
Component (vi) is acid scavenger.Suitable acid scavenger may include metal-oxide, such as magnesium oxide.Acid scavenger
Be it is as known in the art and can including Rhenofit F, Star Mag CX-50, Star Mag CX-150, BLP-3 and
The trade name of MaxOx98LR is commercially available.Rhenofit F are to derive from Rhein Chemie Corporation that Ohio, USA sand is stepped on
The calcium oxide of (Rhein Chemie Corporation of Chardon, OH, USA).Star Mag CX-50 are to derive from the U.S.
Miranda international corporation (the Merrand International Corp.of of state of New Hampshire Portsmouth
Portsmouth, NH, USA) magnesium oxide.MagOX 98LR are the general Lay Mil for deriving from Pennsylvania, America Ken Xiaohuoken
The magnesium oxide of chemical company (Premier Chemicals LLC of W.Conshohocken, PA, USA).BLP-3 is to derive from
The carbon of the Ou meter Ya America company (Omya Americas of Cincinnati, OH, USA) of Ohio, USA Cincinnati
Sour calcium.The amount of acid scavenger (vi) can be in the range of 0.1% to 10% with the gross weight meter of reaction resin and polymer.
Component (vii) is coloring agent (for example, dyestuff or pigment).The example of suitable coloring agent includes white carbon black, Stan-
(which can be from for Tone 40SP03 indigo plants (which can be commercially available from Pu Liwan (PolyOne)) and 33 iron oxide pigments of Colorant BA
Indiana, USA Valparaiso pigment u s company of Cathay (Cathay Pigments (USA),
46383 USA of Inc.Valparaiso, IN) commercially available).The example of coloring agent is as known in the art and special in the U.S.
There is disclosure in profit 4,962,076,5,051,455 and 5,053,442.The coloring agent being added in reaction resin and polymer
Amount depends on many factors, including the type of the other components and selected coloring agent of compositionss, however, the amount is with reaction resin
Can be in the range of 0.001% to 20% with the gross weight meter of polymer.
Component (viii) is resin treatment.Suitable resin treatment can have formula R6Si(OR6)3Or (R6 3Si)2NH and
Its combination, wherein each R6It independently is the univalence hydrocarbyl with 1 to 6 carbon atom.When deployed, resin treatment accounts for reaction
Property resin and total polymer weight less than 1%.
Component (ix) is resist.The example of suitable resist includes benzotriazole, sulfhydryl benzotriazole, sulfydryl benzo
Thiazole, and commercially available resist, such as derive from 2,5-, bis- mercaptos of Vanderbilt company (R.T.Vanderbilt)
Base -1,3,4- thiadiazoles derivatives (826) and alkyl thiadiazoles (484).The amount of component (ix) with
The gross weight meter of reaction resin and polymer can be in the range of 0.05% to 5%.
Component (x) is viscosifier.The example of suitable viscosifier includes alkoxy silane, such as epoxy functional alcoxyl
Base silane or thiol-functional compound；The combination of alkoxy silane and hydroxy-functional polysiloxane；It is hydrosulphonyl functionalized
Compound；Unsaturated compound；Epoxy functional silane；Epoxy functional siloxanes；Combination, such as epoxy functional
The product of silane or epoxy functional siloxanes and hydroxy-functional polysiloxane；Or its combination.It is suitable to increase
Stick is as known in the art and commercially available.For example,A186 is can be from Connecticut, USA Mead that
Ao Sijia special types organosilicon company in uncle (Crompton OSi Specialties of Middlebury,
Connecticut, USA) commercially available β-(3,4- expoxycyclohexyls) ethyl trimethoxy silane.CD9050 is to can be used as
The simple function acid esters of viscosifier, which provides the adhesiveness with metal base and is designed to the compositionss of radiation-hardenable.
CD9050 can be commercially available from Sartomer (Sartomer Co.).SR489D is tridecyl acrylate, and SR395 is third
Olefin(e) acid isodecyl ester, SR257 are stearyl acrylate base ester, and SR506 is isobornyl acrylate, and SR833S is tristane diformazan
Alcohol diacrylate, SR238 are 1,6- hexanediyl esters, and SR351 is trimethylolpropane trimethacrylate, they
All also can be commercially available from Sartomer.It is added to the amount of viscosifier (x) of reaction resin and polymer depending on many
The factor of kind, including other components and reaction resin and the polymerization of selected specific viscosifier, reaction resin and polymer
The final use of thing, however, the amount can be in the range of 0.01% to 5% with the gross weight meter of reaction resin and polymer.
Can be used to promote to include maleic anhydride, methacrylic anhydride and metering system with other suitable viscosifier of the adhesiveness of metal
Acid glycidyl ester.
Component (x) can be insatiable hunger and/or epoxy functional compound.Suitable epoxy functional compound is ability
It is known and commercially available in domain, United States Patent (USP) 4,087,585,5,194,649,5,248,715 and 5,744 is see, for example,
507 (4-5 hurdles).Component (g) may include insatiable hunger and/or epoxy functional alkoxy silane.For example, functionalized alkoxysilane
Alkane can have formula R7 vSi(OR8)(4-v), wherein subscript v is 1,2 or 3, or v is 1.
Each R7Monovalent organic groups independently are, on condition that at least one R7For unsaturated organic group or epoxy radicals official
Organic group can be changed.R7The example of epoxy functional organic group be 3- glycidoxypropyls and (epoxycyclohexyethylSiOi
Base) ethyl.R7Unsaturated organic group example be 3- methacryloxypropyls, 3- acryloxypropyls, and
Unsaturated monovalent hydrocarbon group, such as vinyl, pi-allyl, hexenyl, undecenyl.
Each R8Independently 1 to 4 carbon atoms, or the unsubstituted saturated hydrocarbons group of 1 to 2 carbon atom.R8Show
Example is methyl, ethyl, propyl group and butyl.
The example of suitable epoxy functional alkoxy silane include 3- glycidoxypropyltrimewasxysilanes,
3- glycidoxypropyl triethoxysilanes, (expoxycyclohexyl) ethyldimethoxysilane, (expoxycyclohexyl)
Ethyl diethoxy silane and combinations thereof.The example of suitable unsaturation alkoxy silane include vinyltrimethoxy silane,
Allyltrimethoxysilanis, allyltriethoxysilane, hexenyl trimethoxy silane, undecenyl trimethoxy silicon
Alkane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloxypropyls, 3- acryloyls
Epoxide propyl trimethoxy silicane, 3- acryloxypropyl triethoxysilanes and combinations thereof.Or, suitable viscosifier
Example includes that glycidoxypropyltrimewasxysilane and glycidoxypropyltrimewasxysilane are chelated with aluminum
The combination of thing or zirconium chelate.
Component (x) may include epoxy functional siloxanes, such as hydroxy-end capped polysiloxane with it is as described above
Epoxy functional alkoxy silane product, or hydroxy-end capped polysiloxane and epoxy functional alcoxyl
The physical blending thing of base silane.Component (x) may include epoxy functional alkoxy silane with epoxy functional siloxanes
Combination.For example, the example of component (x) is 3- glycidoxypropyltrimewasxysilanes and hydroxy-end capped methyl ethylene
The mixture of the product of siloxanes and 3- glycidoxypropyltrimewasxysilanes, or 3- glycidoxypropyls
The mixture of trimethoxy silane and hydroxy-end capped methyl vinyl silicone, or 3- glycidoxypropyl trimethoxies
The mixture of silane and hydroxy-end capped methyl ethylene/dimethylsiloxane copolymer.When as physical blending thing rather than
During product, these components individually can be stored in many part box sets (multiple-part kit).
Suitable thiol-functional compound includes organic mercaptan, the silane containing sulfydryl or its combination.Suitably contain sulfydryl
Silane include 3- mercaptopropyl trimethoxysilanes.Suitable thiol-functional compound has in United States Patent (USP) 4,962,076
It is open.Those skilled in the art will recognize that, can for more than one purpose or different purposes by it is as herein described some
Component is added in compositionss.For example, alkoxy silane can be used as viscosifier, filler inorganic agent and/or can condensation reaction
It is used as cross-linking agent in the silicon composition of solidification.
Reaction resin can be formed by one of two methods.
In first method (so-called order additive process), by resin (i) and end-capping reagent (iii) and alkenyl functional
Polysiloxane (iv) is premixed to uniform, is added hydrosilylation catalysts (v) wherein and is mixed product again to equal
Even, wherein catalyst (v) starts the reaction of catalytic resin (i) and end-capping reagent (iii).Temperature is increased to and be enough to realize resin
I the temperature of the reaction of () and end-capping reagent (iii), is such as increased between 35 DEG C and 80 DEG C, such as 40 DEG C.Next, adding
Plus alkoxy-functional organosilicone compounds (ii) and make mixture continue at 80 DEG C of highest one section of reaction it is predetermined when
Between, such as 30 minutes.Now, under full vacuum, be enough to remove at a temperature of any excess blocking agent (iii), such as 140
Product is stripped 30 minutes at DEG C.
In second method or disposable additive process, by resin (i) and alkoxy-functional organosilicone compounds
(ii) premix to uniform with end-capping reagent (iii) and alkenyl functional polysiloxane (iv), now add hydrosilylation
Product is simultaneously mixed to uniform by catalyst (v) again, and wherein catalyst (v) starts the anti-of catalytic resin (i) and end-capping reagent (iii)
Should.Temperature is increased to the temperature of the reaction that be enough to realize resin (i) and end-capping reagent (iii), be such as increased between 35 DEG C with
Between 80 DEG C, such as 40 DEG C.Now, under full vacuum, be enough to remove at a temperature of any excess blocking agent (iii), such as
Product is stripped 30 minutes at 140 DEG C.
The alkoxy-functional organopolysiloxane resins and polymer of the present invention can be used for diversified organosilicon and glue
Mixture application.Alkoxy-functional organopolysiloxane polymer and resin contribute to the allocability of these binding agents, and
The reactive functional groups for being capable of moisturecuring are also provided.
Comparative example
These examples are intended to illustrate the present invention to one of ordinary skill in the art, and should not be construed as restriction power
The scope of the present invention described in sharp claim.Hereinafter described following components used in example.
NMR：Under room temperature (20-22 DEG C) in 16mm without CDCl3 (Isotec) used in Si probes in Mercury VX
Recording solution state on 400MHz spectrogrphs29Si-NMR spectrum and13C-NMR spectrum.By Cr (acac)3(acetopyruvic acid chromium)
(20mM) it is added in NMR samples as relaxation agent.Gather under 79.493MHz29Si NMR spectras, and the long-range navigation by 5Hz
Hereby spectral line broadening is processed.The spectrum because29The long relaxation time of Si cores and it is only semiquantitative, but gather under the same conditions
Spectrum be relatively considered quantitative.Gather under 100.626MHz13C NMR spectras, and composed by the Lorentz of 3Hz
Line is broadening to be processed.For two seed nucleus, generally 256-512 of the addition with 90 ° of pulse widths scannings are enough to realize altogether
Sensitivity；Between the pulses using 6 seconds (29Si) or 12 seconds (13C) postpones.Negative core Overhauser is eliminated using gated decoupling
Effect.Chemical shift is with reference to outside tetramethylsilane (TMS).
I. the component list of example：
DOWSFD-120；The vinyl linear polydimethyl siloxane of 0.13 weight %；
DOWSFD-128；The vinyl linear polydimethyl siloxane of 0.088 weight %；
Methyl hydrogen siloxane；The ring-type SiH methyl hydrogen organosilicon of 1.67 weight %；
DOW2-0707；0.52 weight % platinum of platinum catalyst；
MB2030-(DOWSFD-128/ silica blends)；
MTMS (MTM)；DOWZ6070；
The mixture of OFS-1579/ETS900- methyl triacetoxysilanes and ethyltriacetoxysilane；
Hexamethyldisiloxane (DOW4-2839)；
Tetramethyl divinyl disilazane；(DOWZ-2484)；
(DOWXCF3-6105)-two silica of trimethoxysilylethylgroup group -1,1,3,3- tetramethyls
Alkane (ETM)；
DOW2-5161 end-capping reagent heptamethyltrisiloxanes；
OFS-6030 silane methacryloxypropyl trimethoxy silanes；
OFS-2306 silane trimethoxysilanes (IBTMS)；
Alkoxylated polymers 1 (AP-1)-DOW3-0116 (trimethoxysilylethylgroup group) tetramethyl
Polydimethylsiloxane (the DOW of base disiloxane end-blockingSFD128), about 60,000cps；
Poly- the two of Alkoxylated polymers 2 (AP-2)-(trimethoxysilylethylgroup group) tetramethyl disiloxane end-blocking
Methylsiloxane (DOWSFD-120), about 10,000cps；
Alkoxylated polymers 3 (AP-3) DOW3-1717 (trimethoxysilylethylgroup group) tetramethyl
Polydimethylsiloxane (the DOW of base disiloxane end-blockingSFD-117), about 2000cps；
Alkoxylated polymers 4 (AP-4) DOW3-1719 (trimethoxysilylethylgroup group) tetramethyl
The polydimethylsiloxane of base disiloxane end-blocking, about 500cps；
DOW866 is the binding agent of single part platinum addition curing；
DOW3-6265 is the binding agent of single part platinum addition curing；
DOW3-6265HP is the binding agent of single part platinum addition curing；
The high silanol M of MQ resins 1 (DC407 resins)w17,000-22000g/mol, 3.4 weight % of silanol content can
Derive from the Dow Corning Corporation of Michigan, USA Midland；
The high silanol MQ (6-3444) of 1 high-vinyl of ViMQ resins, 1.9 weight % of contents of ethylene, Mw=17,000-
22000g/mol, 1.5 weight % of silanol content, is available from the Dow Corning Corporation of Michigan, USA Midland；
The low silanol MQ (DOW of 2 high-vinyl of ViMQ resinsPL3444), 1.9 weight of contents of ethylene
Amount %, Mw=17,000-22000g/mol, silanol content 0.3-1.0 weight %, are available from Michigan, USA Midland
Dow Corning Corporation；
Be available from Pennsylvania's Glenn Roc hundred Ma Shi companies (Bimax Inc.of Glen Rock,
Pennsylvania diallyl maleate (DAM))；
It is available from BASF AG (the BASF Corporation of Florham of New Jersey not Lip river Farnham Parker
Park, New Jersey) allyl methacrylate (AMA)；
It is available from Sigma-Aldrich (the Sigma Aldrich of of Wisconsin State Milwaukee
Milwaukee, Wisconsin) Yoshinox BHT (BHT)；
Magnesium oxide (MAGOX SUPER PREMIUM)；It is available from the general Lay Mil of Pennsylvania, America Ken Xiaohuoken
Magnesium product company (19428 USAA of Premier Magnesia, W.Conshohocken, PA)；
BA33 iron oxide pigments；It is available from the pigment u s company of Cathay of Indiana, USA Valparaiso
(Cathay Pigments(USA),Inc.Valparaiso,IN 46383 USA)；
DCBP-50Paste；It is available from Vanderbilt company (the R T of Connecticut, USA Norwalk
Vanderbilt Co.,Norwalk CT 06856 USA)；
Perkadox L-50-PS；The Akzo Nobel Polymer Co., Ltd of Chicago, Illinois, USA
The product of (Akzo Nobel Polymer LLC, Chicago IL USA)；
TAIC；Derive from the Sigma-Aldrich (Sigma-Aldrich of St. Louis
Corp.St.Louis, MO, USA) triallyl isocyanurate；
TYZOR TNBT；The many husband's ketal special catalyst Limited Liabilities for being available from Texas, USA Stafford are public
Department (Dorf Ketal Speciality Catalysts, LLC, 3727Greenbriar Dr., Stafford, TX 77477
USA)；
A-1110 is Silquest A1110, is available from the MomentivePerformanceMaterials of New York, United States Albany
(Momentive Performance Materials Inc,Albany NY USA)；
A-186 is Silquest A186, is available from the MomentivePerformanceMaterials of New York, United States Albany；
TINOPAL OB, derive from BASF AG (the BASF Corporation of New Jersey not Lip river Farnham Parker
100Campus Drive Florham Park, New Jersey 07932.USA) fluorescent whitening agent；
2-mercaptobenzothiazole；It is available from the Sigma-Aldrich of St. Louis；
Trifluoroacetic acid (TFAA), is available from the Sigma-Aldrich of St. Louis；
Trifluoromethayl sulfonic acid, trifluoromethanesulfonic acid (FC-24) are available from the 3M companies (3M of St.Paul, Minnesota
Corporation,St.Paul,MN 55144-1000 USA)；
II. the base material list of example：
AlcladTMAluminum AD Q-Panel 2024T3 types：It is available from the Q-Lab companies (Q- of Ohio, USA Cleveland
Lab Corporation,800Canterbury Rd.,Cleveland,OH 44145 USA)；
III. it is used for the equipment of example：
All blendings hereinafter described are used and are fed with pneumatic barrel pump (Pneumatic pail pump) and with Zenith
The pneumatic high shear mixer of 2.92CC/Rev gear pump-metereds is carried out.Catalyst charge is carried out by Isco 500D syringe pumps.
All extrusioning experiments are in the modularity 30mm corotating manufactured by ShiJi Co., Ltd (Century), the double spiral shells of full engagement
Carry out on bar extruder.Extruder provides power by producing the 15HP AC motors of the screw speed of highest 500rpm.Often
The actual diameter of individual screw rod is 30.7mm and spiral groove depth is 4.8mm.Free space cross-sectional area is 4.77cm2.Machine it is total
Body length is 42 with natural scale:1L/D (12 cylinders), total free processing volume are 477cm3.Screw element used is by the right side
Rotation and left-handed feeding spiro rod and kneading block are constituted.
IV. the viscosity assessment of the adhesive composition comprising alkoxylate resinous polymer blend
A. the synthesis of alkoxylate resinous polymer blend (ARPB)
Alkoxylate resinous polymer blend (ARPB) is prepared by one of two methods：1) individually dividually by alkane
Epoxide agent is subsequently added to single hydrogenation organosilicon end capping reagent (that is, end-capping reagent) in resinous polymer blend (RPB), or
More preferably disposably continuously oxyalkylated reagent and capping reagent are added in RPB.
Sample A is prepared in the following manner：First by component 1 and 3 (referring to table 1 below) mixing 10 minutes.Reaction is by adding
Plus component 2 and be catalyzed.Then make component 1-3 react 30 minutes at 40 DEG C, now addO-on therapy 4 and mixture is continued most
React 30 minutes at high 80 DEG C.Now, product is stripped 30 minutes at 140 DEG C under full vacuum.
Sample is prepared by component 1,3 and 4 being sufficiently mixed 10 minutes and then addO-on therapy 2 and product being mixed 10 minutes
Product B, C and D.Then, product is heated 10 minutes at 40 DEG C.Then temperature is made to rise to 76 DEG C and be kept for 30 minutes.Now, exist
Product is stripped 30 minutes at 140 DEG C under vacuum.The composition of sample A-D collects in table 1：
Table 1
| Component number | Sample A | Sample B | Sample C | Sample D |
| 1. resinous polymer blend RPB1 | 88.8 | 88.8 | 89 | 89 |
| 2. platinum catalyst2 | 0.15 | 0.15 | 0.15 | 0.15 |
| 3.ETM3 | 6.2 | 6.2 | 5.5 | 5 |
| 4. end-capping reagent4 | 5 | 5 | 5.5 | 6 |
| Compositionss property | ||||
| SiH:Vi ratios ETM | 0.6 | 0.6 | 0.53 | 0.48 |
| SiH:Vi ratio end-capping reagents | 0.64 | 0.64 | 0.7 | 0.76 |
| Total SiH/Vi ratios | 1.24 | 1.24 | 1.23 | 1.24 |
1 DOWSFD-120 (the PDMS polymer of ethenyl blocking) and vinylated MQ resins (DOW6-3444) with 45:55 resin and the physical mixture of polymer ratio.6-3444 is for about 1.9 weight %
The silanol of vinyl and 1.8 weight %, such as by29Si-NMR is confirmed.
2 DOW2-0707。
3 DOWXCF3-6105。
4 DOW2-5161。
B. the viscosity assessment of the adhesive composition comprising sample A-D
Then by alkoxylate resinous polymer blend (sample A-D) and silicone fluid and filler (MB2030)
Non-reacted masterbatch mixes to simulate the viscosity of expected binding agent application.Survey on the Brookfield viscometer (HAT) with No. 7 rotors
The respective viscosity of amount gained adhesive composition.
To measure viscosity, in the case of with adhesive sample, rotor is inserted into correct depth.Then, make rotor
Rotated 1 minute with 50 revs/min (rpm), subsequently rotated 1 minute with 100rpm, subsequently rotated two minutes with 10rpm, wherein reading
The viscosity of taking adhesive sample.Then, sample is rotated with 1rpm and read viscosity at 2 minutes.By reading 1rpm values lower
Viscosity determine thixotroping sex rate divided by the lower viscosity for reading of 10rpm values.As a result collect in table 2：
Table 2
Table 2 as a result, it was confirmed that by being added by order or by alkoxy-functional siloxanes obtained in disposable addition
Adhesive composition (comparative sample AA and BB) prepared by reaction resin shows similar viscosity characteristicses.
Additionally, in APRB is kept while total SiH/Vi ratios, reducing oxyalkylated reagent in alkoxylate resin polymerization
Amount in thing blend increases the amount (by sample CC and DD compared with BB) of end-capping reagent simultaneously, causes to introduce their binding agent group
The viscosity of compound is slightly reduced and thixotroping sex index is accordingly reduced.
V. the assessment of adhesive composition
A. methacrylate cluster closes the preparation of organosilicon polymer (MCP-1 and MCP)。
In 50 liters of Turello mixers, load 12kg organosilicon polymer masterbatch (MB2030) (SFD-128/ titanium dioxide
Silicone blends), 6.77kg SFD120 polymer, 1.12kg OS20 silicone fluids (be available from the road of available
The methylsiloxane fluid of Corning Incorporated) and 20.45g OFS-1579 isomer reducing agents.2% oxygen in using blanket of nitrogen
Make mixture inerting and stir 15 minutes.To in the homogenized mix add 6g BHT, 409.7g cyclic methylhydrogensiloxafraction and
965.3g AMA.The mixture of gained is stirred for 20 minutes at room temperature, now adds 26.62g platinum catalysts to mixture
In.Mixture is stirred for 10 minutes, temperature is set to into 60 DEG C afterwards.The temperature is kept for 30 minutes at 60 DEG C, it is subsequently cold
But to more than 40 DEG C and adding 26.62g DAM.Mixture is cool below into 35 DEG C subsequently, adds 182.8g methyl three afterwards
Methoxy silane (MTM).Subsequently heat the mixture to 60 DEG C and kept for 30 minutes, wherein temperature being risen to 80 DEG C and being applied
The vacuum of 55mmHg 40 minutes.The polymer of gained is hereinafter referred to as MCP-1.
To form polymer MCP, in addition to the addition of isomer reducing agent, it then follows with paragraph identical program.
The preparation of B.RPB HS and RPB LS。
By being slowly added 45 parts of DOWSFD-120 polymer (under agitation) is dissolved in diformazan to 55 parts
The resinous polymer blend in following instance is prepared in vinyl MQ resin (ViMQ resins 1 or ViMQ resins 2) in benzene
(RPB HS and RPB LS).The homogeneous solution devolatilization is made at 2mmHg vacuum and 150 DEG C on a rotary evaporator, with shape
(RPB HS are prepared the other resinous polymer blend of composition by ViMQ resins 1；Or RPB LS, prepared by ViMQ resins 2).
Next, 669.7 grams of RPB HS or RPB LS to be blended into 28.3 grams of components 3 and 8.1 grams of components 4 1/4
In quart Ross mixers.Add 7.55 grams of components 5 and 0.76 gram of component 6 optionally in the mixture and mix 15 minutes.
Then to the process blend of addO-on therapy in the mixture 5 and 6, and the mixture is blended 15 minutes, is then heated to 60
DEG C keep 30 minutes.Finally, heat is made to increase to 120 DEG C and mixture is placed under vacuum.The compositionss (shown in table 3) point of gained
ARPB-E, ARPB-F and ARPB-G are not labeled as.
Table 3
C. hot radical cured silicone adhesive composition is prepared for assessment
In 1 quart of Ross mixer, mix following components, while cooling is to maintain 25 DEG C or lower temperature, so as to
Adhesive composition is formed, as shown in table 4.
Table 4
| MCP-1 | 71.75 |
| ARBP (E, F or G) | 19.34 |
| RBM-9020 modifying agent | 2.95 |
| OFS-6030 silane | 1.97 |
| TAIC | 0.49 |
| TYZOR TNBT | 0.62 |
| A-1110 | 0.1 |
| A186 | 0.6 |
| MBT | 0.15 |
| OFS-2306 silane | 1.96 |
| OFS-1719 silane | 0.1 |
| TINOPAL OB | 0.02 |
Next, (deriving from the TA instrument companies (TA of Delaware State Newcastle using Ares parallel-plate rheometers
Instruments, 159Lukens Drive, New Castle, DE G2 type Ares flow graphs 19720)) with two kinds of shearing speed
Rate (0.1s-1And 1s-1) monitoring formed by table 4 and be listed in the table below the binding agent in 5 and change with days of ageing at room temperature
Viscosity.As a result collect in table 5 and 6：
Table 5
(0.1s
-1
Shear rate)
Table 6
(1s
-1
Shear rate)
As table 5 and 6 confirms, the low upsilonanol form (ARPB-E and ARPB-F) of ARPB provides the higher silane with ARPB
Alcohol form (ARPB-G) compares the viscosity of reduction.
Next, applying adhesive to AlcladTMAluminium base (being available from Aluminum Company of America (Alcoa)) and at 85 DEG C
Solidification 20 minutes the adhesive layer thickness with 8 mils.At room temperature half sample is estimated and makes which aging, while will
Remaining sample is placed in pressure cooker tester (PCT), is kept for 24 hours in 1 additional atmospheric pressure, and is entered after aging
Row assessment.Have evaluated the lap shear adhesion characteristic of appropriate aging coated substrate peak stress (with pound/square inch
(PSI) represent), as a result collect in table 7.
Table 7
As demonstrated in Table 7, introducing isomer reducing agent in adhesive composition causes and AlcladTMThe adhesion of aluminium base
It is suitable that property is compared with the sample without isomer reducing agent.
D. the assessment of the distribution property of hot radical cured silicone adhesive composition
Next, the distribution property of the various hot radical solidification composition fillings of assessment.
Material in table 8 is being available from into the Fu Laike Imtech of South Carolina, United States Lan Delamu
It is cold common in the Hauschild Speedmixer DAC150.1FV-K of (FlackTek Inc, Landrum, SC 29356USA)
It is mixed.
Table 8
Before allocability assessment is carried out, also the component in table 9 is mixed in speedmixer.
Table 9
12 AP3-DOW3-1717- (trimethoxysilylethylgroup group) tetramethyl disiloxane end-blocking
Polydimethylsiloxane (DOWSFD-117), about 2000cps.
Allotter is injected using EFD 1000-XL and (is available from the Nuo Xin EFD companies of Rhode Island,USA east Providence
(Nordson EFD, East Providence, RI 02914USA)) it is allocated and webbing inspection.Injected by 30ml EFD
Device distributes the material being compared under 50 pounds/square inch of air pressure.
Grading is based under pressure applied the subjective grading of the ability for controlling bead of adhesive (bead).The grading
Reflect trend and length of any globule when pressure applied terminates.Even if with the excellent solidification to various base materials and
Adhesiveness, if but can not routinely distribute bead of adhesive or round dot on base material in timely mode, can also prevent business
On employing.
As demonstrated in Table 9, ARPB-1 defined above improves distributivity in the case where engineering propertiess are not lost.Which also carries
For secondary curing mechanism, by the mechanism, glue because oxygen quenching acts on any surface for causing during radical UV curing system can be overcome
Property.It should also be noted that alkoxy-functional is very desirable for mineral and metal surface are adhered to.
E. the assessment of the engineering propertiess of hot radical cured silicone adhesive composition
1 inch × 3 inches of various base materials of panel (being prepared for 3 samples) is cleaned with acetone.Using being suitable to the application
(the baud industry of Oregon bank ratio is public for the Spheriglass spacer balls (spacer bead) of (that is, 8 mils (200 microns))
Department (Potters Industries Inc.350North Baker Drive, Canby, OR 97013-0607)) set up bonding
Layer.Larger tack coat uses 20 Mil wires.
3/8 inch of binder is used for into two kinds of separation methods, with fixing substrate during curing.Hardening time and temperature exist
Describe in detail in following result.In 5566 tonometeies of Instron (the Instron Global Headquarters of Massachusetts promise Wood
(Instron Worldwide Headquarters, 825University Ave., Norwood, MA 02062-2643)) on
Tested with 2 inch/minutes.
Table 10
11Derive from Ohio, USA Cleveland Q-Lab companies (Q-Lab Corporation, 800.,
Cleveland, OH44145 USA) Alclad aluminum AD Q-Panel 2024T3 types.
123105PBT：It is available from Ticona North American Corp. (Ticona North of Kentucky State Florence
America, Florence, KY polybutylene terephthalate (PBT) 41042)3105。
13LCP：Be available from Houston, Texas, United States Su Wei chemical companies (Solvay Chemicals,
77098 USA of Houston, Texas) liquid crystal polymer
14PA66：Be available from New Jersey not Lip river Farnham Parker BASF AG (BASF Corpration,
07932 USA of FlorhamPark, NJ) polyamide
15PC：It is available from the primary radical innovations Plastics Company (SABIC of sand of Massachusetts, United States pittsfield
InnovativePlastics Pittsfield, MA 01201, USA) Merlon
16PE：Polyethylene, middle-high density PE (PEX), the Lloyd's for being available from North Carolina Moore Si Weier are public
Department (28117 USA of Lowes, Mooresville, NC)
17FR-4：The promise Praxair for being available from U.S. Iowa Persian Te Weier steps click up to company (Norplex-
Micarta, Postville, Iowa, USA) epoxy glass fiber laminates.
As illustrated by table 10, adhesive composition (3 binding agent of table with MCP-1) of the invention is for aluminium base
Enough adhesivenesses and cohesion are shown with plastic basis material, and to adhere to the sole binder compositionss of polyethylene.
The disclosure is described by exemplary approach, it should be understood that term used is intended to be essentially descriptive word, and
It is not restricted word.Obviously, according to teaching above, many modifications of the disclosure and modification are possible.Therefore, should
Understand, within the scope of the appended claims, the disclosure can not be implemented as specifically describing.
Claims (17)
1. a kind of alkoxy-functional organopolysiloxane resins and polymer, which includes the product of following components reaction：
I () includes R3SiO1/2Unit and SiO4/2The alkenyl functional silicone resin of unit,
Wherein each R independently is the univalence hydrocarbyl with 1 to 6 carbon atom, on condition that at least one R is thiazolinyl,
Wherein described R3SiO1/2Unit and SiO4/2The mol ratio of unit has the value in the range of 0.5/1 to 1.5/1,
(ii) there is the hydrogen atom of at least one silicon bonding in molecular end and there is formula HSi (R3)2OSi(R3)2CH2CH2SiR3 z(OR3)3-zFunctionalized with alkoxysilane organosilicone compounds, wherein each R3Independently be with 1 to
The monovalent hydrocarbon of 6 carbon atoms and wherein subscript z are 0 or 1；
(iii) according to formula R2 3SiO-(R2 2SiO)s-SiR2 2H or R2 3SiO-(R2 2SiO)t-(HR2SiO)-SiR2 3Or its combination
End-capping reagent, wherein each R2It independently is alkyl and wherein subscript s and t has the value in the range of 0 to 10 respectively；And
(iv) polysiloxane of each molecule averagely with least 2 aliphatic series unsaturation organic groups；
The reaction is carried out in the presence of (v) hydrosilylation catalysts.
2. alkoxy-functional organopolysiloxane resins according to claim 1 and polymer, wherein the thiazolinyl official
1 weight % of the silanol content less than alkenyl functional silicone resin (i) gross weight of silicone resin (i) can be changed.
3. alkoxy-functional organopolysiloxane resins and polymer according to claim 1 or claim 2, wherein
Alkenyl functional silicone resin (i) is with the weight average molecular weight in the range of 12,000 to 30,000g/mol.
4. alkoxy-functional organopolysiloxane resins and polymer according to claim 1 or claim 2, wherein
Alkenyl functional silicone resin (i) is with the weight average molecular weight in the range of 17,000 to 22,000g/mol.
5. alkoxy-functional organopolysiloxane resins according to claim 1 and polymer, wherein R2For methyl.
6. alkoxy-functional organopolysiloxane resins according to claim 1 and 2 and polymer, wherein the thiazolinyl
At most 60 weight % of the thiazolinyl of functionalized silicone resin (i) are anti-with the hydrogen atom of the silicon bonding of component (ii)
Should.
7. alkoxy-functional organopolysiloxane resins according to claim 1 and 2 and polymer, wherein the thiazolinyl
At least 40 weight % of the thiazolinyl of functionalized silicone resin (i) are anti-with the hydrogen atom of the silicon bonding of component (iii)
Should.
8. alkoxy-functional organopolysiloxane resins according to claim 1 and 2 and polymer, poly- have wherein described
Organic siloxane (iv) is according to formula (I) R4 2R5SiO(R4 2SiO)a(R4R5SiO)bSiR4 2R5Or according to formula (II) R4 3SiO(R4 2SiO)c
(R4R5SiO)dSiR4 3Or its combination, wherein each R4The monovalent organic groups without aliphatic degree of unsaturation independently are, each R5
Aliphatic unsaturation organic group independently is, subscript a has the meansigma methodss in the range of 2 to 1000, and subscript b has 0 to 1000 model
Meansigma methodss in enclosing, subscript c is with the meansigma methodss in the range of 0 to 1000, and subscript d is with average in the range of 4 to 1000
Value, and wherein 10≤(a+b)≤1000 and 10≤(c+d)≤1000.
9. alkoxy-functional organopolysiloxane resins according to claim 1 and 2 and polymer, wherein the alcoxyl
The amount vinyl content of base functionalization organopolysiloxane resins and polymer accounts for the alkoxy-functional organopolysiloxane resins
With 0.6 to 2.2 weight % of the gross weight of polymer.
10. alkoxy-functional organopolysiloxane resins according to claim 1 and 2 and polymer, wherein the alkane
The silanol content of epoxide functionalization organopolysiloxane resins and polymer accounts for the alkoxy-functional organopolysiloxane
0.3 to 2.2 weight % of the gross weight of resin and polymer.
11. alkoxy-functional organopolysiloxane resins according to claim 1 and 2 and polymer, wherein the alkane
Epoxide functionalization organopolysiloxane resins and polymer are also selected from acid scavenger, coloring agent, resin treatment comprising at least one
Agent, resist, viscosifier and its any combination of other component.
12. alkoxy-functional organopolysiloxane resins according to claim 11 and polymer, wherein the resin
Inorganic agent includes R6Si(OR6)3、(R6 3Si)2NH and combinations thereof, wherein each R6It independently is the list with 1 to 6 carbon atom
Valency alkyl.
A kind of 13. methods for forming alkoxy-functional organopolysiloxane resins and polymer, including：
(1) while reacting following components：
I () includes R3SiO1/2Unit and SiO4/2The alkenyl functional silicone resin of unit, wherein each R independently are with 1
To the univalence hydrocarbyl of 6 carbon atoms, on condition that at least one R is thiazolinyl,
Wherein described R3SiO1/2Unit and SiO4/2The mol ratio of unit has 0.5/1 to 1.5/1 value,
(ii) there is the hydrogen atom of at least one silicon bonding in molecular end and there is formula HSi (R3)2OSi(R3)2CH2CH2SiR3 z(OR3)3-zFunctionalized with alkoxysilane organosilicone compounds, wherein each R3Independently be with 1 to
The monovalent hydrocarbon of 6 carbon atoms and wherein subscript z are 0 or 1,
(iii) according to formula R2 3SiO-(R2 2SiO)s-SiR2 2H or R2 3SiO-(R2 2SiO)t-(HR2SiO)-SiR2 3Or its combination
End-capping reagent, wherein each R2It independently is alkyl and wherein subscript s and t has the value in the range of 0 to 10 respectively,
(iv) polysiloxane of each molecule averagely with least 2 aliphatic series unsaturation organic groups；And
(v) hydrosilylation catalysts, to obtain the product of step (1)；And
(2) under vacuo the product of step (1) is stripped to remove any excessive end-capping reagent (iii) and shape
Into the alkoxy-functional organopolysiloxane resins and polymer.
14. a kind of method for forming alkoxy-functional organopolysiloxane resins and polymer, including：
(1) while reacting following components：
I () includes R3SiO1/2Unit and SiO4/2The alkenyl functional silicone resin of unit, wherein each R independently are with 1
To the univalence hydrocarbyl of 6 carbon atoms, on condition that at least one R is thiazolinyl and wherein described R3SiO1/2Unit and SiO4/2Unit
Mol ratio with 0.5/1 to 1.5/1 value,
(iii) according to formula R2 3SiO-(R2 2SiO)s-SiR2 2H or R2 3SiO-(R2 2SiO)t-(HR2SiO)-SiR2 3Or its combination
End-capping reagent, wherein each R2It independently is alkyl and wherein subscript s and t independently has the value in the range of 0 to 10 respectively,
(iv) polysiloxane of each molecule averagely with least 2 aliphatic series unsaturation organic groups, and
(v) hydrosilylation catalysts, to obtain product；And
(2) (ii) is had into the hydrogen atom of at least one silicon bonding in molecular end and there is formula HSi (R3)2OSi(R3)2CH2CH2SiR3 z(OR3)3-zFunctionalized with alkoxysilane organosilicone compounds introduce step (1) the product
And the product of step (2) is obtained, wherein each R3It independently is the monovalent hydrocarbon with 1 to 6 carbon atom and wherein subscript z is
0 or 1；And
(3) excessive end-capping reagent (iii) is stripped to form the alkoxy-functional from the product of step (2) under vacuo
Change organopolysiloxane resins and polymer.
15. methods according to claim 13 or claim 14, wherein alkenyl functional silicone resin (i)
The atomic reaction of hydrogen of at most 60 weight % of the thiazolinyl and the silicon bonding of component (ii).
16. methods according to claim 13 or 14, wherein the thiazolinyl of alkenyl functional silicone resin (i)
At least 40 weight % and component (iii) the silicon bonding atomic reaction of hydrogen.
17. methods according to claim 13 or 14, also include at least one other component being incorporated into formed alkane
Epoxide functionalization organopolysiloxane resins and polymer, at least one component in addition are selected from acid scavenger, coloring agent, tree
Fat inorganic agent, resist, viscosifier and its any combinations.
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| US201361763129P | 2013-02-11 | 2013-02-11 | |
| US61/763,129 | 2013-02-11 | ||
| PCT/US2014/015619 WO2014124388A1 (en) | 2013-02-11 | 2014-02-10 | Alkoxy-functional organopolysiloxane resin and polymer and related methods for forming same |
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| WO2014124388A1 (en) | 2014-08-14 |
| US20160002513A1 (en) | 2016-01-07 |
| TWI613258B (en) | 2018-02-01 |
| EP2954021A1 (en) | 2015-12-16 |
| US9862867B2 (en) | 2018-01-09 |
| JP6323838B2 (en) | 2018-05-16 |
| JP2016507628A (en) | 2016-03-10 |
| KR102186328B1 (en) | 2020-12-03 |
| KR20150117263A (en) | 2015-10-19 |
| TW201446879A (en) | 2014-12-16 |
| CN104968748A (en) | 2015-10-07 |
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